US3850609A - Polychloro parathio phenols - Google Patents

Polychloro parathio phenols Download PDF

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US3850609A
US3850609A US00288220A US28822072A US3850609A US 3850609 A US3850609 A US 3850609A US 00288220 A US00288220 A US 00288220A US 28822072 A US28822072 A US 28822072A US 3850609 A US3850609 A US 3850609A
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phenol
trichloro
tetrachloro
compound
carbon atoms
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US00288220A
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W Bissinger
D Hardies
J Lavanish
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Wyeth Holdings LLC
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PPG Industries Inc
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system

Definitions

  • phenols which are effective as miticides and which also often possess herbicidal, insecticidal, and/or fungicidal properties.
  • nis3or4;and R is lower alkyl, lower alkenyl, or lower cycloalkyl.
  • Subclasses within the scope of the above formula are trichloro-4-(alkylthio)phenol, tetrachloro-4-(alkylthiol-phenol, trichloro-4-(alkenylthio)phenol, tetrachloro-4-(alkenylthio)phenol, trichloro-4-(cycloalkylthio)phenol, and tetrachloro-4-(cycloalkylthio)phenol.
  • the trichloro-4-(alkylthio)phenols and the tetrachloro- 4-(alkylthio)phenols are preferred. 7
  • R in the above formula is lower alkyl, it usually contains from I to 8 carbon atoms.'lt may be either straight or branched. Most often R is methyl or ethyl. Methyl is preferred.
  • R When R is lower alkenyl, it generally contains from 3 to 8 carbon atoms. Ally] is most often used.
  • R When R is lower cycloalkyl, it typically contains from 3 to 8 carbon atoms. Most often it contains 5 to 8 carbon atoms. Cyclohexyl is preferred.
  • the chlorine atoms may be arranged in either the 2,3,6-positions or the 2,3,5-positions.
  • the former arrangement is preferred.
  • n 3 or 4.
  • the members of this class are 2,3,5-trichloro-4-(methylthio)phenol, 2,3,6-trichloro-4-(methylthio)phenol, and 2,3,5,6-tetrachloro-4-(methylthio)phenol.
  • Another method of preparation may be achieved by the reaction, in the presence of a base, of the appropriately chlorine substituted thiocyanatophenol and an organic halide of the formula RX wherein R is lower alkyl, lower alkenyl, or lower cycloalkyl and X is ahalogen, usually chlorine, bromine, or iodine.
  • the chlorine substituted thiocyanatophenol starting material may be prepared by reacting l) the appropriately chlorine substituted phenol having an unsubstituted para-site with (2) ammonium thiocyanate or an alkali metal thiocyanate and (3) an oxidizing agent such as chlorine or bromine.
  • the phenols of this invention may be prepared by the hydrolysis of a compound represented by the structural formula wherein n is 3 or 4 and R is as hereinbefore defined, in the presence of a solvent and at least one base selected from the group consisting of alkali metal hydroxide and alkaline earth metal hydroxide. Sodium hydroxide or potassium hydroxide is most often used. Potassium hydroxide is preferred.
  • Exemplary solvents include the alcohols having from 1 to 10 carbon atoms. The preferred solvents are the tertiary alcohols having from 4 to 10 carbon atoms.
  • solvents examples include methyl alcohol, ethyl alcohol, isopropyl alcohol, tertbutyl alcohol, l-methylamyl alcohol, tert-amyl alcohol, normal hexyl alcohol isohexyl alcohol, 2-ethylhexyl alcohol, l, l -diethylpropyl alcohol, normal decyl alcohol, l,l-diethyl-3-methylamyl alcohol. Tertiary amyl alcohol or tertiary butyl alcohol is preferred. Mixtures of solvents and/or bases are within contemplation.
  • R is methyl.
  • Hydrolysis is typically carried out at a temperature ranging from about 30C. to about 200C. although other temperatures can be used. Most often the temperature is in the range of 80C. to 150C.
  • the reaction is ordinarily carried out at atmospheric pressure although greater or lesser pressures may be used if desired. The reaction progresses satisfactorily when the reaction mixture is heated to reflux, usually at atmospheric pressure.
  • EXAMPLE 1 A 300 ml. two-necked flask is equipped with a magnetic stirrer, thermometer, and dropping funnel. The flask is immersed in a wet ice bath and charged with 100 m1. of methyl alcohol, 6.0 g. of 2,3,5,6- tetrachlorophenol, and 22 g. of potassium thiocyanate. To this solution at C. C. a solution of 4.3 ml. of bromine in 25 ml. of methyl alcohol (saturated with sodium bromide) is added dropwise over a period of 1.5 hours. During the addition a precipitate forms and the mixture becomes quite thick. After an additional two On taking a melting point of this product, it starts to melt at 165C., then darkens and resolidifies above 185C. The product is analyzed for carbon, hydrogen,
  • a 50 ml. flask is charged with 4.2 g. of 2,3,5,6-tetrach1oro-4-thiocyanatophenol, 2,2 g. of methyl iodide, and 20 ml. of methanol.
  • a solution of 3.0 g. of 85 percent potassium hydroxide in 10 ml. of water is added dropwise with stirring over a period of 70 minutes. After stirring at room temperature for 2 hours, the mixture is stripped to dryness on a rotary film evaporator. The residue is dissolved in 20 ml. of
  • the aqueous mixture is extracted once with 150 ml. of diethyl ether and three times with 100 ml. portions of diethyl ether.
  • the combined ether extract is dried over sodium sulfite, filtered, and stripped on a rotary evaporator thereby yielding 28 g. of yellow solid.
  • Gas chromatopgraphic analysis of methylene chloride solu- .tions of the yellow solid show the yellow solid to be about 60 percent 2,3,6-trichloro-4-thiocyanatophenol and the rest 2,3,6-trichlorophenol.
  • the yellow solid is redissolved in 30 ml. of methyl alcohol along with 40 g. of potassium thiocyanate. To the stirred mixture at 3C 8C.
  • a ml. flask is charged with 4.1 g. of 2,3,6- trichloro-4-thiocyanatophenol, 2,3 g. of methyl iodide, and 30 ml. of methanol.
  • a magnetic stirring bar is added and the flask is fitted with a pressure equalized addition funnel charged with 2.7 g. of potassium hydroxide in 15 ml. of water.
  • the potassium hydroxide solution is added dropwise over a period of 30 minutes with stirring. After 2 hours the mixture is concentrated under vacuum until about 25 ml. of solutin remained.
  • the product may be depicted as having the structural formula:
  • EXAMPLE 111 The compound 2,3,5-trichloro-4-thiocyanatophenol is prepared in a manner similar to that of Example 11 using 2,3,5-trichlorophenol in lieu of 2,3,6- trichlorophenol.
  • the compound 2,3,5-trichloro-4-(methylthio)phenol is prepared in a manner similar to that of Example 11 using 4.1 g. of 2,3,5-trichloro-4- thiocyanatophenol in place of 4.1 g. of 2,3,6-trichloro- 4-thiocyanatophenol.
  • the product may be depicted as having the structural formula:
  • Example 1V illustrates another way in which 2,3,5,6- tetrachloro-4-(methy1thio)phenol may be prepared.
  • the product may be depicted as having the structural formula:
  • the phenols of this invention may be used to kill or retard development of mites.
  • the phenol is applied directly. to the mites. In another embodiment the phenol is applied to regions where mites are likely to be found in order to kill the mites present or to preclude mite populations from becoming established.
  • ppm parts per million by weight
  • Typical formulations contain from about 10 to about 1,000 ppm. Often formulations containing from about 10 to about ppm are used.
  • the type of formulation used may vary. Solutions and suspensions of the phenol are effective. The usual method of applying solutions or suspensions is to drench the area of application. Sprays', showers, mists, and dips may be used for this purpose. When some of the more active phenols are used, particularly at the higher concentrations, a complete drenching is not necessary. Mists are often used where a drench is not desired. 1
  • the phenol formulations of the invention may also be applied in the form of a powder or dust.
  • These powders or dusts may contain diluents such as, for example, aluminum silicate, bentonite, calcium carbonate, calcium silicate, diatomaceous silica, hydrated lime, pulverized limestone, montmorillonite, pulverized phosphate rock, silica, talc, or vermiculite.
  • the concentration of the phenol compound in the formulation and the total amount applied will vary depending upon the particular phenol being employed and the particular mite being confronted. Other facts such as season of the year, environmental conditions,
  • EXAM PLE V Potted horticultural bean plants Phaseolus vulgaris L.
  • two-spotted spider mites Tetrany'chus urticae 24 hours prior to treatment, insuring establishment of adults and deposition of eggs at the time of treatment.
  • a stock acetone emulsion is prepared having the following composition by weight: 99.75 percent acetone, 0.20 percent sorbitan trioleate (Span 85), and 0.05 percent sorbitan monooleate polyoxyalkylene derivative (Tween 80).
  • Test compound is dissolved in a por tion of the stock acetone emulsion.
  • Deionized water is added to yield a concentrated test solution containing about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80.
  • the amount of test compound dissolved in the stock acetone emulsion is such that when diluted with deionized water the concentrated test solution has the highest concentration (usually 1,000 ppm) of test compound used in the tests.
  • Solutions which are prepared by diluting the concentrated test solution with a mixture of deionized water and stock acetone emulsion, which mixture contains about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80. Thus, all test solutions always contain about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80, irrespective of the concentration of test compound.
  • Infested host plants are dipped into agitated solutions of the test compound, allowed to air dry, provided with a subterranean water source, and held for observation.
  • test plants Three test plants are used for each unit of treatment.
  • Weeds may also be killed by bringing the weeds and a phytocidal amount of the phenolinto mutual contact, as for example, by applying the phenol to the weeds.
  • the pheno] is applied to the soil where weeds are likely to be found in order to preclude weeds from becoming established.
  • the formulations used as phytocides are similar in all material respects to those described above for miticidal purposes.
  • concentration of the phenol in the formulation and the total amount applied will vary depending upon the particular phenol being employed and the particular weed being confronted. Other factors such as season of the year, environmental conditions, and stage of weed development all have their effect.
  • Exemplary application rates are from about 0.1 to about 100 pounds per acre. Usually the rate will range from about 0.1 to about 20 pounds per acre. Rates of from about 0.5 to about 10 pounds per acre are most often used.
  • Examples VII through XIII the following procedure was used: For pre-emergence testing, appropriate weed species are seeded in individual disposable 3-inch square containers containing about 2 inches of soil.
  • sand After spraying directly on the seeded soil surface, a small amount of sand, usually about 1/8 to H4 inch in depth, is applied to cover the'seeds.
  • weed species are seeded by growth-time requirement schedules in individualdisposable 3 inch square containers cona solvent mixture of 90 percent acetone, 8 percent 10 methanol, and 2 percent dimethylformamide by vol;
  • Yellow Nutsedge (Cyperus esrulentus L.) 5 8 Wild Oats (Avena falua L.) 2 9 Jimsonweed (Datum srramonium L.) 0 l0 Velvetleaf (Abulilan Iheophrasli Medic.) 2 l() .lohnsongrass (Sorghum halepense Pers.) 4 8 Lambsquarter (Chenopodium album L.) l0 Mustard (Brassim kaher L. C. Wheeler Var. pinnalifldu L. C.
  • Insoluble compounds are formulated as wettable powders and diluted with water and wetting agent before application.
  • Each carrying tray of pre-emergence and/or post emergence containers placed on a conveyor belt having a linear speed of 1.5 miles per hour, trips a microswitch which, in turn, activates a solenoid valve and releases the compound under test.
  • the compound under test is discharged as sprays at a rate of 50 gallons per acre.
  • Containers used for pre-emergence testing are then watered.
  • Containers for both pre-emergence and post-emergence testing are then removed to the greenhouse and held for observation.
  • Pre-emergence and post-emergence treatments are observed daily for interim response, final observations usually being made 14 days after treatment. Any treatments inducing significant response are held beyond the 14-day observation period until such responses can be confirmed.
  • Each result is reported as an Injury Rating which is represented as follows: 0 no visible effect; l, 2, 3 slight injury, plant usually recovered with little or no reduction in top growth; 4, 5, or 6 moderate injury, plants usually recovered but with reduced top growth; 7, 8, or 9 severe injury, plants EXAMPLE Vlll Test Compound: 2,3,5,6-Tetrachloro-4-(methylthio)phenol Observations made 21 days after application o)phenol Observations made 14 days after application Test Plant Post-Emergence 1 5 lb/A 2 lh/A l lh/A Yellow Nutsedge (Cyperur erculenms L.) 7 2 0 Wild Oats (Arena falua L.) 10 7 3 .limsonweed (Dalura slramonium L.) l0
  • Yellow Nutsedge (Cyperus esculenlus L.) 8 Wild Oats (Avena falua L.) 0 8 .limsonweed (Dalura slramonium L.) l0 .Iohnsongrass (Sorghum halepense Pers.) 4 l Lambsquarter (Chenopodium album L.) 0 Mustard (Brassica kaber L. C. Wheeler Var. pinnaliflda L. C.
  • Flax (Linum ulsilatissl'mum L.)
  • Peppergrass (from tubers) Peppergrass (Lapl'dum pampexlre [L.) R. Br.)
  • Chickweed (Slellaria media [L.] Cyrillo) Cocklehur (Xanlllillm pennrylvanicum Wallr) Giant Foxtail (Selaria faberii Herrm.)
  • Hedge Bindweed (Convolvulus Sapium L.)
  • a method of killing weeds which comprises applying to the soil in the vicinity of the weeds a phytocidal amount of a compound represented by the formula:
  • n 3 or 4; and R is lower alkyl, lower alkenyl, or lower cycloalkyl. 2. The method of claim 1 wherein R is selected from the group consisting of lower alkyl containing from 1 represented by the structural formula:
  • R is lower alkyl containing from 1 to 8 carbon atoms.
  • n 3 or 4.
  • a method of killing weeds which comprises bringing into mutual contact the weeds and a phytocidal amount of a compound represented by the structural formula:
  • n 3 or 4.
  • R is selected from the group consisting of lower alkyl containing from 1 to 8 carbon atoms, lower alkenyl containing from 3 to 8 carbon atoms, and lower cycloalkyl containing from 3 to 8 carbon atoms.
  • R is lower alkyl containing from 1 to 8 carbon atoms.
  • n 3 or 4.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Chlorinated (alkylthio)phenols, chlorinated (alkenylthio)phenols, and chlorinated (cycloalkythio)phenols are described which are useful as miticides. These phenols often possess herbicidal, insecticidal, and/or fungicidal properties. Examples of these compounds are 2,3,5,6-tetrachloro-4(methylthio)-phenol and 2,3,6-trichloro-4-(methylthio)phenol.

Description

United States Patent [1 1 Bissinger et a1.
[451 Nov. 26 1974 POLYCHLORO PARATHIO PHENOLS [75] inventors: William E. Bissinger, Akron; Donald E. Hardies, Wadsworth; Jerome M. Lavanish, Akron, all of Ohio [73] Assignee: PPG Industries, Inc., Pittsburgh, Pa.
[22] Filed: Sept. 11, 1972 [21] Appl. No.: 288,220
Related U.S. Application Data [62] Division of Ser. No. 76,651, Sept. 28, 1970, Pat. No.
[52] U.S. Cl. 71/98 [51] Int. Cl A0ln 9/12 [58] Field of Search 71/98 [56] References Cited UNITED STATES PATENTS 3,282,979 11/1966 Reifschneider et a1. 71/98 X Primary ExaminerLewis Gotts Assistant Examiner-Catherine L. Mills Attorney, Agent, or Firm-George G. Morris [57] ABSTRACT 18 Claims, N0 Drawings .1 POLYCHLORO PARATH IO PHENOLS This is a division of application Ser. No. 76,651, filed Sept. 28, 1970, now US. Pat. No. 3,723,538.
In accordance with this invention, there are provided phenols which are effective as miticides and which also often possess herbicidal, insecticidal, and/or fungicidal properties.
Phenols here contemplated may be represented by I the formula:
wherein nis3or4;and R is lower alkyl, lower alkenyl, or lower cycloalkyl.
Subclasses within the scope of the above formula are trichloro-4-(alkylthio)phenol, tetrachloro-4-(alkylthiol-phenol, trichloro-4-(alkenylthio)phenol, tetrachloro-4-(alkenylthio)phenol, trichloro-4-(cycloalkylthio)phenol, and tetrachloro-4-(cycloalkylthio)phenol. The trichloro-4-(alkylthio)phenols and the tetrachloro- 4-(alkylthio)phenols are preferred. 7
When R in the above formula is lower alkyl, it usually contains from I to 8 carbon atoms.'lt may be either straight or branched. Most often R is methyl or ethyl. Methyl is preferred.
When R is lower alkenyl, it generally contains from 3 to 8 carbon atoms. Ally] is most often used.
When R is lower cycloalkyl, it typically contains from 3 to 8 carbon atoms. Most often it contains 5 to 8 carbon atoms. Cyclohexyl is preferred.
When the value of n is 3 in the above formula, the chlorine atoms may be arranged in either the 2,3,6-positions or the 2,3,5-positions. The former arrangement is preferred.
An important class falling within the generic invention is represented by the formula:
wherein the value of n is 3 or 4. The members of this class are 2,3,5-trichloro-4-(methylthio)phenol, 2,3,6-trichloro-4-(methylthio)phenol, and 2,3,5,6-tetrachloro-4-(methylthio)phenol.
Compounds which exemplify the phenols of the invention are:
2,3,5-trichloro-4-(methylthio)phenol 2,3,5-trichloro 4-(ethylthio)phenol 2,3,5-trichloro-4-(propylthio)phenol 2,3,5-trichloro-4-(isopropylthio)phenol 2,3,5-trichloro-4-(butylthio)phenol 2,3,5-trichloro-4-(sec-butylthio)phenol 2,3,5-trichloro-4-(isobutylthio)phenol I 2,3,5-trichloro-4-(2,2,3,3-tetramethylbutylthio)- phenol 2,3 ,5-trichloro-4-(allylthio )phenol 2,3 ,5-trichloro-4-( 3-pentenylthio )phenol 2,3 ,5-trichloro-4-( cyclopropylthio )phenol 2,3 ,5-trichloro-4-( cyclopentylthio )phenol 2,3 ,5-trichloro-4-(cyclohexylthio )phenol 2,3,5-trichloro-4-(cycloheptylthio)phenol 2,3 ,5-trichloro-4-( cyclooctylthio )phenol 2, 3 ,6-trichloro-4-(methylthio )phenol 2,3 6-trichloro-4-( ethylthio )phenol 2 ,3 ,6-trichloro-4-(propylthio )phenol 2 ,3 ,6-trichloro-4-( isopropylthio )phenol 2,3 ,6-trichloro-4-( butylthio )phenol 2,3 ,6-trichloro-4-( sec-butylthio )phenol 2 ,3 ,6-trichloro-4-( isobutylthio )phenol 2 ,3 ,6-trichloro-4-( tert-butylthio )phenol 2,3,6-trichloro-4-(pentylthio)phenol 2,3,6-trichloro-4-( l ,Z-dimethylpropylthio )phenol 2,3,6 trichloro-4-(hexylthio)phenol 2,3,6-trichloro-4-(4-methylpentylthio)phenol 2,3,6-trichloro-4-( l ,3-dimethylbutylthio)phenol 2,3,6-trichloro-4-(2-ethylbutylthio)phenol 2,3,6-trichloro-4-(heptylthio)phenol 2,3,6-trichloro-4-(S-methylhexylthio)phenol 2,3,6-trichloro-4-(2,2-dimethylpentylthio)phenol 2,3,6-trichloro-4-( l ,2,2-trimethylbutylthio)phenol 2,3,6-trichloro-4-( l ,2,3-trimethylbutylthio)phenol 2,3,6-trichloro-4-( l-ethyl-2,2-dimethylpropylthio)- phenol 2,3,6-trichloro-4-( l ,Z-diethylpropylthio)phenol 2,3,6-trichloro-4-(octylthio)phenol 2,3,6-trichloro-4-(Z-methylheptylthio)phenol. 2,3,6-trichloro-4-( l ,4-dimethylhexylthio)phenol 2,3,6-trichloro-4-(2,2,3-trimethylpentylthio)phenol 2,3,6-trichloro-4-(2-ethyl-2-methylpentylthio)- phenol 2,3,6-trichloro-4-( l,2,2,3-tetramethylbutylthio)- phenol 2,3 ,6-trichloro-4-( 2,2-diethylbutylthio )phenol 2,3,6-trichloro-4-( l-isopropyl-2-methylbutylthio phenol 2,3 ,6-trichloro-4-( allylthio )phenol 2,3,6-trichloro-4-(2-pentenylthio)phenol 2,3,6-trichloro-4-(3-hexenylthio)phenol 2,3,6-trichloro-4-(cyclopropylthio)phenol 2,3,6-trichloro-4-(cyclobutylthio)phenol 2,3,6-trichloro-4-(cyclopentylthio)phenol 2,3,6-trichloro-4-( cyclohexylthio )phenol 2 ,3 ,6-trichloro-4-( cycloheptylthio )phenol 2,3 ,6-trichloro-4-( cyclooctylthio)phenol 2,3,5,6-tetrachloro-4-(methylthio)phenol 2,3 ,5 ,6-tetrachloro-4-( ethylthio )phenol 2,3 ,5 ,6-tetrachloro-4-(propylthio)phenol 2,3,5,6-tetrachloro-4-(isopropylthio)phenol 2,3 ,5 ,6-tetrachloro-4-( butylthio )phenol 2,3,5,6-tetrachloro-4-(sec-butylthio)phenol 2,3,5 ,6-tetrachloro-4-( isobutylthio)phenol 2,3,5 ,6-tetrachloro-4-( tert-butylthio)phenol 2,3 ,5 ,6-tetrachloro-4-(pentylthio )phenol 2 ,3 ,5 ,6-tetrachloro-4-( 2-methylbutylthio )phenol 2,3,5 ,6-tetrachloro-4-( 2,2-dimethylpropylthio)- phenol 2,3,5 ,6-tetrachloro-4-( hexylthio)phenol 2 ,3 ,5 ,6-tetrachloro-4-( 3-methylpentylthio )phenol 2,3,5,6-tetrachloro-4-( l ,Z-dimethylbutylthio)phenol 2,3,5 ,6-tetrachloro-4-( 2,3-dimethylbutylthio )phenol 2,3 ,5 ,6-tetrachloro-4-( 2,3-dimethylhexylthio)phenol 2,3,5 ,6-tetrachloro-4-( 2,4-dimethylhexylthio)phenol 2,3,5,6-tetrachloro-4-( l,2,4-trimethylpentylthio)- phenol 2,3,5 ,6-tetrachloro-4-( 2,2,4-trimethylpentylthio)- phenol 2,3,5,6-tetrachloro-4-( 2,4,4-trimethylpentylthio phenol 2,3 ,5 ,6-tetrachloro-4-( 2,3,4-trimethylpentylthio)- phenol 2,3,5 ,6-tetrachloro-4-( 3-ethyl-3-methylpentylthio)- phenol 2,3,5 ,6-tetrachloro-4-( 2,2,3,B-tetramethylbutylthio)- phenol 2,3,5 ,6-tetrachloro-4-( l,2,2,3-tetramethylbutylthio phenol 2,3,5 ,6-tetrachloro-4-( l-ethyl-2,Z-dimethylbutylthio )-phenol 2,3,5,6-tetrachloro-4-( l,Z-diethylbutylthio)phenol 2,3,5,6-tetrachloro-4-( 2,2-diethylbutylthio)phenol 2,3,5,6-tetrachloro-4-( l-propyl-2-methylbutylthio)- phenol 2,3,5,6-tetrachloro-4- I -isopropyl-2-methylbutylthio)-phenol. 2,3,5,6-tetrachloro-4-( l-isopropyl-2-methylpropylthio)-phenol 2,3,5,6-tetrachloro-4-(allylthio)phenol 2,3,5,6-tetrachloro-4-(2-pentenylthio)phenol 2,3,5 ,6-tetrachloro-4-( 3-pentenylthio )phenol 2,3,5,6-tetrachloro-4-(3-hexenylthio)phenol 2,3,5,6-tetrachloro-4-(4-hexenylthio)phenol 2,3,5,6-tetrachloro-4-(cyclopropylthio)phenol 2,3,5,6-tetrachloro-4-(cyclobutylthio)phenol 2,3,5,6-tetrachloro-4-(cyclopentylthio)phenol 2,3,5,6-tetrachloro-4-(cyclohexylthio)phenol 2,3 ,5 ,6-tetrachloro-4-(cycloheptylthio )phenol 2,3,5,6-tetrachl0ro-4-(cyclooctylthio)phenol These phenols may be prepared by the reaction, in the presence of a base, of the appropriately chlorine substituted thiocyanatophenol and an alcohol of the formula ROI-l wherein R is lower alkyl, lower alkenyl, or lower cycloalkyl.
Another method of preparation may be achieved by the reaction, in the presence of a base, of the appropriately chlorine substituted thiocyanatophenol and an organic halide of the formula RX wherein R is lower alkyl, lower alkenyl, or lower cycloalkyl and X is ahalogen, usually chlorine, bromine, or iodine.
The chlorine substituted thiocyanatophenol starting material may be prepared by reacting l) the appropriately chlorine substituted phenol having an unsubstituted para-site with (2) ammonium thiocyanate or an alkali metal thiocyanate and (3) an oxidizing agent such as chlorine or bromine.
Reactions similar to the above are shown in U.S. Pat. Nos. 3,231,623; 3,246,039; 3,274,257; 3,282,979; 3,303,206; and 3,303,209.
The phenols of this invention may be prepared by the hydrolysis of a compound represented by the structural formula wherein n is 3 or 4 and R is as hereinbefore defined, in the presence of a solvent and at least one base selected from the group consisting of alkali metal hydroxide and alkaline earth metal hydroxide. Sodium hydroxide or potassium hydroxide is most often used. Potassium hydroxide is preferred. Exemplary solvents include the alcohols having from 1 to 10 carbon atoms. The preferred solvents are the tertiary alcohols having from 4 to 10 carbon atoms. Examples of these solvents are methyl alcohol, ethyl alcohol, isopropyl alcohol, tertbutyl alcohol, l-methylamyl alcohol, tert-amyl alcohol, normal hexyl alcohol isohexyl alcohol, 2-ethylhexyl alcohol, l, l -diethylpropyl alcohol, normal decyl alcohol, l,l-diethyl-3-methylamyl alcohol. Tertiary amyl alcohol or tertiary butyl alcohol is preferred. Mixtures of solvents and/or bases are within contemplation. In a preferred embodiment R is methyl. Hydrolysis is typically carried out at a temperature ranging from about 30C. to about 200C. although other temperatures can be used. Most often the temperature is in the range of 80C. to 150C. The reaction is ordinarily carried out at atmospheric pressure although greater or lesser pressures may be used if desired. The reaction progresses satisfactorily when the reaction mixture is heated to reflux, usually at atmospheric pressure.
Preparation of the contemplated phenols is illustrated by Examples I IV.
EXAMPLE 1 A 300 ml. two-necked flask is equipped with a magnetic stirrer, thermometer, and dropping funnel. The flask is immersed in a wet ice bath and charged with 100 m1. of methyl alcohol, 6.0 g. of 2,3,5,6- tetrachlorophenol, and 22 g. of potassium thiocyanate. To this solution at C. C. a solution of 4.3 ml. of bromine in 25 ml. of methyl alcohol (saturated with sodium bromide) is added dropwise over a period of 1.5 hours. During the addition a precipitate forms and the mixture becomes quite thick. After an additional two On taking a melting point of this product, it starts to melt at 165C., then darkens and resolidifies above 185C. The product is analyzed for carbon, hydrogen,
nitrogen, and chlorine. The results expressed in percent by weight are shown in Table l.
Table 1 Analysis of 2,3,5,fi-tetrachlow-44hiocyanatophenol C H N Cl Calculated for C,HCl NOS 29.1 0.35 4.85 49.2
Found 28.96 0.42 4.86 48.62
A 50 ml. flask is charged with 4.2 g. of 2,3,5,6-tetrach1oro-4-thiocyanatophenol, 2,2 g. of methyl iodide, and 20 ml. of methanol. A solution of 3.0 g. of 85 percent potassium hydroxide in 10 ml. of water is added dropwise with stirring over a period of 70 minutes. After stirring at room temperature for 2 hours, the mixture is stripped to dryness on a rotary film evaporator. The residue is dissolved in 20 ml. of
. water. This solution is poured into a mixture of 10 ml.
of concentrated hydrochloric acid and 25 g. of ice. The white precipitate which forms is separated from the bulk of the liquid by filtration and dried. The residue weighs 3.8 grams. Recrystallization from a mixture of normal hexane and benzene gives 2.4 g. of pale yellow crystals having a melting point range of 121C. to 123.5C. The product is 2,3,5,6-tetrachloro-4-(methylthio)pheno1 and may be depicted as having the structural formula:
- l Cl SCI-l EXAMPLE 11' A 500 ml. three-necked flask is equipped with a mechanical stirrer, a thermometer, and a dropping funnel. The flask is immersed in a wet ice bath and charged with 200 ml. methyl alcohol, 20.0 g. of 2,3,6- trichlorophenol, and 35.0 g. of potassium thiocyanate. To the stirred mixture at 4C. 8C. a solution of 1 1.0 ml. of bromine in 40 ml. of methyl alcohol (saturated with sodium bromide) is added dropwise over a period of one hour. The mixture is stirred an additional half hour and then poured into 1000 ml. of water. The aqueous mixture is extracted once with 150 ml. of diethyl ether and three times with 100 ml. portions of diethyl ether. The combined ether extract is dried over sodium sulfite, filtered, and stripped on a rotary evaporator thereby yielding 28 g. of yellow solid. Gas chromatopgraphic analysis of methylene chloride solu- .tions of the yellow solid show the yellow solid to be about 60 percent 2,3,6-trichloro-4-thiocyanatophenol and the rest 2,3,6-trichlorophenol. The yellow solid is redissolved in 30 ml. of methyl alcohol along with 40 g. of potassium thiocyanate. To the stirred mixture at 3C 8C. a solution of 1 1.0 ml. of bromine in 40 ml. of methyl alcohol (saturated with sodium bromide) is added dropwise over a period of 40 minutes. After stirring an additional hour, the reaction mixture is extracted once with 150 ml. of diethyl ether and three times with 100 ml. portions of diethyl ether. The combined ether extract is dried over sodium sulfite, filtered, and stripped on a rotary evaporator thereby yielding 21.0 g. of yellow solid. Gas chromatographic analysis of this yellow solid shows it to be more than percent 2,3,6-trichloro-4-thiocyanatophenol. This yellow solid is dissolved in hot benzene, filtered while hotto remove a dark red semi-solid, and cooled to give 14.4 g. of light yellow 2,3,6-trichloro-4-thiocyanatophenol, melting point range 128C. 129C.,
A ml. flask is charged with 4.1 g. of 2,3,6- trichloro-4-thiocyanatophenol, 2,3 g. of methyl iodide, and 30 ml. of methanol. A magnetic stirring bar is added and the flask is fitted with a pressure equalized addition funnel charged with 2.7 g. of potassium hydroxide in 15 ml. of water. The potassium hydroxide solution is added dropwise over a period of 30 minutes with stirring. After 2 hours the mixture is concentrated under vacuum until about 25 ml. of solutin remained.
This is poured into a mixture of 20 ml. of concentrated hydrochloric acid and 25 g. of ice. The tan solid which separates is filtered, washed with two 25 ml. portions of water, and dried to give 3.8 g. of tan powder. Recrystallization from a mixture of normal hexane and chloroform gives, after filtration and drying, 1.5 g. of tan nee- 5 dles having a melting point range of 128C. 129C.,
(broad, OH) and nuclear magnetic resonance signals at 2.498 (singlet, 31-1) and 7.225 (singlet, ll-l). The spectra are consistent with 2,3,6-trichloro-4-(methylthio)phenol. The product is analyzed for carbon, hydrogen, and chlorine. The results expressed in percent by weight are shown in Table 2.
' Table 2 Analysis of.2,3,6-trichloro-4-(methylthio)phenol C H Cl Calculated for C-,H Cl,OS 34.5 2.0 43.7
Found 338 2.0 44.5
The product may be depicted as having the structural formula:
SCH
EXAMPLE 111 The compound 2,3,5-trichloro-4-thiocyanatophenol is prepared in a manner similar to that of Example 11 using 2,3,5-trichlorophenol in lieu of 2,3,6- trichlorophenol. The compound 2,3,5-trichloro-4-(methylthio)phenol is prepared in a manner similar to that of Example 11 using 4.1 g. of 2,3,5-trichloro-4- thiocyanatophenol in place of 4.1 g. of 2,3,6-trichloro- 4-thiocyanatophenol.
The product may be depicted as having the structural formula:
Example 1V illustrates another way in which 2,3,5,6- tetrachloro-4-(methy1thio)phenol may be prepared.
EXAMPLE IV addition of 50 ml. of water gives a cloudy solution which is washed with two 25 ml. portions of benzene. The aqueous solution is heated on a steam bath until enough residual benzene is driven off for the solution to become clear. The solution is allowed to cool. Concentrated hydrochloric acid is then added until no further cloudiness appeared. An oil separates which is dissolved in benzene. The benzene solution is dried and concentrated on a rotary film evaporator to give 4.7 g. of waxy brown crystals. They are dissolved in a refluxing mixture of normal hexane and benzene, filtered while still hot, and allowed to cool. The crystals which form are filtered and dried. They weigh 1.8 g. and have a melting point range of 108C. 116C. A second recrystallization from a mixture of normal hexane and chloroform gives 1.1 g. of tan crystals with a melting point range of 119C. l20.5C.,
.. Eli-.2 29. 22 32-.
Table 3 Analysis of 2,3,5,6-Tetrachloro4(methylthio)phenol C H Cl Calculated for 30.3 1.5 51.2
C-,H Cl,OS
Found 29.3 1.5 51.9
The product may be depicted as having the structural formula:
SCH
In general, the phenols of this invention may be used to kill or retard development of mites.
In one embodiment the phenol is applied directly. to the mites. In another embodiment the phenol is applied to regions where mites are likely to be found in order to kill the mites present or to preclude mite populations from becoming established.
Usually formulations containing from about 5 to about 2,000 parts per million by weight (ppm) of the phenol compound are applied. Typical formulations contain from about 10 to about 1,000 ppm. Often formulations containing from about 10 to about ppm are used.
The type of formulation used may vary. Solutions and suspensions of the phenol are effective. The usual method of applying solutions or suspensions is to drench the area of application. Sprays', showers, mists, and dips may be used for this purpose. When some of the more active phenols are used, particularly at the higher concentrations, a complete drenching is not necessary. Mists are often used where a drench is not desired. 1
The phenol formulations of the invention may also be applied in the form of a powder or dust. These powders or dusts may contain diluents such as, for example, aluminum silicate, bentonite, calcium carbonate, calcium silicate, diatomaceous silica, hydrated lime, pulverized limestone, montmorillonite, pulverized phosphate rock, silica, talc, or vermiculite.
The concentration of the phenol compound in the formulation and the total amount applied will vary depending upon the particular phenol being employed and the particular mite being confronted. Other facts such as season of the year, environmental conditions,
and stage of mite development all have their effect.
The following specific embodiments illustrate, by way of example, the basic principles of the present invention.
EXAM PLE V Potted horticultural bean plants (Phaseolus vulgaris L.) at growth stage when primary leaves are approximately 1 inch long are infested with two-spotted spider mites (Tetrany'chus urticae) 24 hours prior to treatment, insuring establishment of adults and deposition of eggs at the time of treatment.
A stock acetone emulsion is prepared having the following composition by weight: 99.75 percent acetone, 0.20 percent sorbitan trioleate (Span 85), and 0.05 percent sorbitan monooleate polyoxyalkylene derivative (Tween 80). Test compound is dissolved in a por tion of the stock acetone emulsion. Deionized water is added to yield a concentrated test solution containing about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80. The amount of test compound dissolved in the stock acetone emulsion is such that when diluted with deionized water the concentrated test solution has the highest concentration (usually 1,000 ppm) of test compound used in the tests. Solutions which are prepared by diluting the concentrated test solution with a mixture of deionized water and stock acetone emulsion, which mixture contains about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80. Thus, all test solutions always contain about 10 percent acetone, 0.020 percent Span 85, and 0.0050 percent Tween 80, irrespective of the concentration of test compound.
Infested host plants are dipped into agitated solutions of the test compound, allowed to air dry, provided with a subterranean water source, and held for observation.
Three test plants are used for each unit of treatment.
Table 4 Miticidal Effectiveness of 2,3,5,6-Tetrachloro-4- (methylthio)phenol Against Two-Spotted Spider Mite (Tetranychus urlicae) The procedure of Example V is repeated using 2,3,6- trichloro-4-(methylthio)phenol as the test compound. The results are shown in Table 5.
Table 5 Miticidal Effectiveness of 2,3,6-Trichloro-4- (methylthio)pheno1 Against Two-Spotted Spider Mite (-Telranychus urlicae) Concentration Percent Mortalitv ppm Initial Ovicidal Residual 1,000 100 0 I00 500 g 100 0 100 250 I00 0 96 0 Trace Many of the phenols of the present invention possess properties which make them useful as phytocides, as for example, herbicides. Weeds may be killed by applying to the soil in the vicinity of the weeds a phytocidal amount of the phenol. Weeds may also be killed by bringing the weeds and a phytocidal amount of the phenolinto mutual contact, as for example, by applying the phenol to the weeds. In another embodiment the pheno] is applied to the soil where weeds are likely to be found in order to preclude weeds from becoming established.
The formulations used as phytocides are similar in all material respects to those described above for miticidal purposes. The concentration of the phenol in the formulation and the total amount applied will vary depending upon the particular phenol being employed and the particular weed being confronted. Other factors such as season of the year, environmental conditions, and stage of weed development all have their effect. Exemplary application rates are from about 0.1 to about 100 pounds per acre. Usually the rate will range from about 0.1 to about 20 pounds per acre. Rates of from about 0.5 to about 10 pounds per acre are most often used.
In Examples VII through XIII the following procedure was used: For pre-emergence testing, appropriate weed species are seeded in individual disposable 3-inch square containers containing about 2 inches of soil.
After spraying directly on the seeded soil surface, a small amount of sand, usually about 1/8 to H4 inch in depth, is applied to cover the'seeds.
For post-emergence testing, appropriate weed species are seeded by growth-time requirement schedules in individualdisposable 3 inch square containers cona solvent mixture of 90 percent acetone, 8 percent 10 methanol, and 2 percent dimethylformamide by vol;
usually did not recover; l0 all plants killed. Deviations from the above procedure, if any, are reported with the data.
EXAMPLE Vll Test Compound: 2,3,5,6-Tetrachloro-4-(methylthio)phenol Pre-Emergence Observations made If) days after application Post-Emergence Observations made 13 days after application Pre- Post Test Plant Emergence Emergence 5 lb./A 5 lb./A
Yellow Nutsedge (Cyperus esrulentus L.) 5 8 Wild Oats (Avena falua L.) 2 9 Jimsonweed (Datum srramonium L.) 0 l0 Velvetleaf (Abulilan Iheophrasli Medic.) 2 l() .lohnsongrass (Sorghum halepense Pers.) 4 8 Lambsquarter (Chenopodium album L.) l0 Mustard (Brassim kaher L. C. Wheeler Var. pinnalifldu L. C. Wheeler) 8 10 Yellow Foxtail (Serlariu gluuca Beauv.) 2 9 Barnyardgrass (ECIliIlOLIl/lltl crusgulli Beauv.) 2 7 Crabgrass (Digimriu sanguinulis Scop.) 8 8 Buckwheat (Polygmlum ((HH'UIVMIIIS L.) 2 IO Morning Glory (mixture of lpumoeu purpurea Roth and lpomoeu Iiederacea .lacq.) 5 9 Red Kidney Bean (Phaseulus vulgaris L.)
Primary Leaf Stage l0 Trifoliate Leaf Stage l0 Untreated Controls Normal Normal ume. Insoluble compounds are formulated as wettable powders and diluted with water and wetting agent before application.
Each carrying tray of pre-emergence and/or post emergence containers, placed on a conveyor belt having a linear speed of 1.5 miles per hour, trips a microswitch which, in turn, activates a solenoid valve and releases the compound under test. The compound under test is discharged as sprays at a rate of 50 gallons per acre. Containers used for pre-emergence testing are then watered. Containers for both pre-emergence and post-emergence testing are then removed to the greenhouse and held for observation.
Pre-emergence and post-emergence treatments are observed daily for interim response, final observations usually being made 14 days after treatment. Any treatments inducing significant response are held beyond the 14-day observation period until such responses can be confirmed. Each result is reported as an Injury Rating which is represented as follows: 0 no visible effect; l, 2, 3 slight injury, plant usually recovered with little or no reduction in top growth; 4, 5, or 6 moderate injury, plants usually recovered but with reduced top growth; 7, 8, or 9 severe injury, plants EXAMPLE Vlll Test Compound: 2,3,5,6-Tetrachloro-4-(methylthio)phenol Observations made 21 days after application o)phenol Observations made 14 days after application Test Plant Post-Emergence 1 5 lb/A 2 lh/A l lh/A Yellow Nutsedge (Cyperur erculenms L.) 7 2 0 Wild Oats (Arena falua L.) 10 7 3 .limsonweed (Dalura slramonium L.) l0 l0 l0 Velvetleaf (Ahulilon lheaphrarli Medic.) l0 l0v l0 Johnsongrass (Sorghum Iialepense Pers.) 3 2 l Mustard (Brarsica kaber L. C. Wheeler Var. pinnaufida L. C. Wheeler) l0 l0 9 Yellow Foxtail (Selaria glauca Beauv.) l0 7 6 Barnyardgrass (Evlrinuclrlua crusgalli Beauv.) 8 7 6 Crabgrass .(Digilnria sanguinalis Scop.) l0 9 7 Buckwheat '(Palygonum convolvulus L.) l0 l0 8 Morning Glory (mixture of lpomoea purpurea Roth and lpomoea hederacea .lacq.) l0 l0 9 Red Kidney Bean (Phaseolus vulgaris L.)
Primary Leaf Stage 2 2 2 Trifoliate Leaf Stage 9 5 2 Untreated Controls Normal Normal Normal EXAMPLE X Test Compound: 2,3,6-Trichloro-4-(methylthio)- phenol Pre-Emergence Observations made 16 days after application Post-Emergence Observations made 13 days after application Pre Post- Test Plant Emergence Emerence 5 lb./A 5 lb./A
Yellow Nutsedge (Cyperus esculenlus L.) 8 Wild Oats (Avena falua L.) 0 8 .limsonweed (Dalura slramonium L.) l0 .Iohnsongrass (Sorghum halepense Pers.) 4 l Lambsquarter (Chenopodium album L.) 0 Mustard (Brassica kaber L. C. Wheeler Var. pinnaliflda L. C. Wheeler) 6 l0 Velvetleaf (Abulilon Illeophrasli Medic.) 2 l0 Yellow Foxtail (Selaria glauca Beauv.) 2 I 2 Barnyardgrass (Echinochlua crusgalli Beauv.) 2 5' Crabgrass Digitaria sanguinalis Scop.) 7 8 Buckwheat (Polygonunl convolvulus L.) 0 10 Morning Glory (mixture of lpumoea purpurea Roth and lponwea hederazea .Iacq.) 8 Red Kidney Bean (Plraseulus vulgaris L.)
Primary Leaf Stage 10 Trifoliate Leaf Stage l0 Untreated Controls Normal Normal EXAMPLE XI Test Compound: 2,3,6-Trichloro-4-(methylthio)- phenol Observations made 21 days after application EXAMPLE XII Test Compound: 2,3 ,5 ,6-Tetrachloro-4-(methylthio )phenol Observations made 14 days after application Post-Emergence Test Plant 2 lb/A 0.5 lb/A Sugar Beet (Bela vulgaris L.) )0 8 Corn (Zea mays L.) 2 l Oats (Arena saliva L.) 2 3 Red Clover (Trij'alium pralellse L.) 10 9 Soybean (Glycine max [L.] Merr.) 5 5 Cotton (Gorrypium llirsulum L.) 5 l Wheat (Trilicum avslirum L.) 5 2 Peanut (Arachis hypogaea L.) 2 l Rice (Oryza raliva L.) 6 3 Kentucky Bluegrass (Pun prau'nsis L.) l l Alfalfa (Medit'agu .ruliva L.) l() 9 Flax (Linum ulrilalisximum L.) 4 2 Pigweed (Amara/Imus re'truflexus L.) 5 2 Wild Oats (Arena falua L.) l() Ouackgrass (Agropymll repens [L.] Beauv.)
C ontinued w Test p 2 lb/A 0.5 lb/A Russian Thistle (Salsa/a kali L. Var. Tenuifnlia Tausch) (from seed) )0 l0 Plorsenettle (Sulanunl carolinense L.) (from seed) 7 5 Purple Nutsedge ((yperus mlumlus L.)
' (from tubers) U 0 Peppergrass (Lepidum mmpeslre [L] R. Br.) 8 5 Chickweed (Slellaria media [L.] Cyrillo) 9 7 Cocklebur (Xanlllium pvnnrylrallicum Wallr.) l0 4 Giant Foxtail (Seraria faberii Herrm.) l 0 .lohnsongrass (Sorghum halepenre [L.] Pers.)
(from rhizomes) O 0 Hedge Bindweed (Convulvulur Sepium L.)
(from rhizomes) 7 4 Quackgrass (Agropyron repens [L.] Beauv.)
(from rhizomes) 0 0 Post-Emergence Test Plant 2 lb/A 0.5 lb/A Sugar Beet (Bela vulgaris L.)
Corn (Zea mays L.)
Oats (Avena saliva L.)
Red Clover (Trlfalium pralense L.)
Soybean (Glycine max [L.] Merr.)
Cotton (Gassypium hirsulum L.)
Wheat (Trl'licum aeslivum L.)
Peanut (Arazhis Ilypagaea L.)
Rice (Oryza saliva L.)
Kentucky Bluegrass (Poa pralenris L.)
Alfalfa (Medicagv saliva L.)
Flax (Linum ulsilatissl'mum L.)
Pigweed (Amaranlhus relraflexus L.)
Wild Oats (Arena falua L.)
Russian Thistle (Salrala kali L. Var. Tenuifolia Tausch) (from seed) Horsenettle (Solarium caralinense L.) (from seed) 7 Purple Nutsedge (Cyperus rqlundus L.)
(from tubers) Peppergrass (Lapl'dum pampexlre [L.) R. Br.)
Chickweed (Slellaria media [L.] Cyrillo) Cocklehur (Xanlllillm pennrylvanicum Wallr) Giant Foxtail (Selaria faberii Herrm.)
.lohnsongrass (Sorghum llalepenre [L.] Pers.)
(from rhizomes) Hedge Bindweed (Convolvulus Sapium L.)
(from rhizomes) (from rhizomes) O While the invention has been described with reference to certain illustrative embodiments, it is not intended that it shall be limited thereby except insofar as appears in the accompanying claims.
We claim:
1. A method of killing weeds which comprises applying to the soil in the vicinity of the weeds a phytocidal amount of a compound represented by the formula:
wherein n is 3 or 4; and R is lower alkyl, lower alkenyl, or lower cycloalkyl. 2. The method of claim 1 wherein R is selected from the group consisting of lower alkyl containing from 1 represented by the structural formula:
to 8 carbon atoms, lower alkenyl containing from 3 to 8 carbon atoms, and lower cycloalkyl containing from 3 to 8 carbon atoms.
3. The method of claim 1 wherein R is lower alkyl containing from 1 to 8 carbon atoms.
4. The method of claim 1 wherein the compound is represented by the structural formula:
sen
wherein n is 3 or 4.
5. The method of claim 4 wherein the compound is 2,3,6-trichloro-4-(methylthio)phenol.
'6. The method of claim 4 wherein the compound is 2,3,5,6-tetrachloro-4-(methylthio)phenol.
7. A method of killing weeds which comprises bringing into mutual contact the weeds and a phytocidal amount of a compound represented by the structural formula:
wherein n is 3 or 4.
11. The method of claim 10 wherein the compound is 2,3,6-trichloro-4-(methylthio)phenol.
12. The method of claim 10 wherein the compound is 2,3,5,6-tetrachloro-4-(methylthio)phenol.
13. A method of precluding the establishment of a weed population in the soil comprising applying to the soil an effective amount of a compound represented by the structural formula:
wherein n is 3 or 4; and R is lower alkyl, lower alkenyl, or lower cycloalkyl.
14. The method of claim 13 wherein R is selected from the group consisting of lower alkyl containing from 1 to 8 carbon atoms, lower alkenyl containing from 3 to 8 carbon atoms, and lower cycloalkyl containing from 3 to 8 carbon atoms.
15. The method of claim 13 wherein R is lower alkyl containing from 1 to 8 carbon atoms.
16. The method of claim 13 wherein the compound is represented by the structural formula:
SCH3
wherein n is 3 or 4.
17. The method of claim 16 wherein the compound is 2,3,6-trichloro-4-(methylthio)phenol.
18. The method of claim 16 wherein the compound is 2,3,5,6-tetrachloro-4-(methylthio)phenol. V

Claims (18)

1. A METHOD OF KILLING WEEDS WHICH COMPRISES APPLYING TO THE SOIL IN THE VICINITY OF THE WEEDS A PHYTOCIDAL AMOUNT OF A COMPOUND REPRESENTED BY THE FORMULA:
2. The method of claim 1 wherein R is selected from the group consisting of lower alkyl containing from 1 to 8 carbon atoms, lower alkenyl containing from 3 to 8 carbon atoms, and lower cycloalkyl containing from 3 to 8 carbon atoms.
3. The method of claim 1 wherein R is lower alkyl containing from 1 to 8 carbon atoms.
4. The method of claim 1 wherein the compound is represented by the structural formula:
5. The method of claim 4 wherein the compound is 2,3,6-trichloro-4-(methylthio)phenol.
6. The method of claim 4 wherein the compound is 2,3,5,6-tetrachloro-4-(methylthio)phenol.
7. A method of killing weeds which comprises bringing inTo mutual contact the weeds and a phytocidal amount of a compound represented by the structural formula:
8. The method of claim 7 wherein R is selected from the group consisting of lower alkyl containing from 1 to 8 carbon atoms, lower alkenyl containing from 3 to 8 carbon atoms, and lower cycloalkyl containing from 3 to 8 carbon atoms.
9. The method of claim 7 wherein R is lower alkyl containing from 1 to 8 carbon atoms.
10. The method of claim 7 wherein the compound is represented by the structural formula:
11. The method of claim 10 wherein the compound is 2,3,6-trichloro-4-(methylthio)phenol.
12. The method of claim 10 wherein the compound is 2,3,5,6-tetrachloro-4-(methylthio)phenol.
13. A method of precluding the establishment of a weed population in the soil comprising applying to the soil an effective amount of a compound represented by the structural formula:
14. The method of claim 13 wherein R is selected from the group consisting of lower alkyl containing from 1 to 8 carbon atoms, lower alkenyl containing from 3 to 8 carbon atoms, and lower cycloalkyl containing from 3 to 8 carbon atoms.
15. The method of claim 13 wherein R is lower alkyl containing from 1 to 8 carbon atoms.
16. The method of claim 13 wherein the compound is represented by the structural formula:
17. The method of claim 16 wherein the compound is 2,3,6-trichloro-4-(methylthio)phenol.
18. The method of claim 16 wherein the compound is 2,3,5,6-tetrachloro-4-(methylthio)phenol.
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Publication number Priority date Publication date Assignee Title
US3959487A (en) * 1972-09-11 1976-05-25 Ppg Industries, Inc. Control of mites with polychloro parathio phenols

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US3282979A (en) * 1963-06-17 1966-11-01 Dow Chemical Co Phenolic thioethers

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Publication number Priority date Publication date Assignee Title
US3282979A (en) * 1963-06-17 1966-11-01 Dow Chemical Co Phenolic thioethers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959487A (en) * 1972-09-11 1976-05-25 Ppg Industries, Inc. Control of mites with polychloro parathio phenols

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